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EP 0 520 551 B1 |
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EUROPEAN PATENT SPECIFICATION |
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Mention of the grant of the patent: |
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27.03.1996 Bulletin 1996/13 |
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Date of filing: 16.06.1992 |
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Liquid detergent compositions
Flüssige Detergenszusammensetzungen
Compositions détergentes liquides
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Designated Contracting States: |
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CH DE ES FR GB IT LI NL SE |
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Priority: |
28.06.1991 GB 9114045
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Date of publication of application: |
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30.12.1992 Bulletin 1992/53 |
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Proprietors: |
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- UNILEVER N.V.
NL-3013 AL Rotterdam (NL) Designated Contracting States: CH DE ES FR IT LI NL SE
- UNILEVER PLC
London EC4P 4BQ (GB) Designated Contracting States: GB
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Inventor: |
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- Thompson, Ian
I-20071 Casalpusterlengo (Milan) (IT)
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Representative: Kan, Jacob Hendrik, Dr. |
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Unilever N.V.
Patent Division
P.O. Box 137 NL-3130 AC Vlaardingen NL-3130 AC Vlaardingen (NL) |
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References cited: :
EP-A- 0 130 609 GB-A- 1 230 413
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EP-A- 0 164 058 GB-A- 2 121 072
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Note: Within nine months from the publication of the mention of the grant of the European
patent, any person may give notice to the European Patent Office of opposition to
the European patent
granted. Notice of opposition shall be filed in a written reasoned statement. It shall
not be deemed to
have been filed until the opposition fee has been paid. (Art. 99(1) European Patent
Convention).
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[0001] The present invention relates to liquid detergent compositions, more especially to
those which have a pearlescent appearance.
[0002] It is well known to endow a pearlescent appearance to surfactant based-products so
that they may convey an aesthetic appeal to the consumer. This is done quite often
with cosmetic products such as shampoos. However, it is also sometimes done with products
associated with the cleaning of fabrics, for example rinse conditioners, when it is
desired to convey an impression of gentleness and care for the fabrics.
[0003] For the formulation of so-called light duty liquids (sometimes called fine wash liquids),
ie liquid products for washing delicate fabrics such as woolens, eg by hand, it is
known to use significant concentrations of alkylbenzene sulphonates (ABS) in the liquid
product. Recent concerns about possible detrimental effects of ABS on the environment
have lead to a desire to minimise the amount of ABS in such formulations. One alternative
anionic surfactant which might be a suitable replacement for at least part of the
ABS is a primary alkyl sulphate (PAS) surfactant.
[0004] There are several possible ways of making such a composition pearlescent. One way
is to incorporate small mica crystals. However, to keep these crystals dispersed in
the product, it is necessary to formulate it to have good solid-suspending properties.
If the liquid is to remain pourable whilst being able to suspend solids, then it needs
to have a suitable liquid crystalline phase. That in turn necessitates using relatively
high concentrations of detergent active materials (surfactants) and usually also,
relatively high concentrations of electrolytes. Such concentrated formulations tend
to be unduly harsh for use with delicate fabrics.
[0005] Therefore, for light duty products it is necessary to use a long-chain organic pearlescer
which can be crystallised-out in the formulation to give a good dispersion of crystals
of the appropriate size and shape. Examples of such pearlescers are ethylene glycol
monostearate and the corresponding distearate. Unfortunately, when used in products
containing significant amounts of PAS, the crystallisation process yields poor crystals
which give an inadequate pearlescent effect.
[0006] GB 2,121,072 discloses aqueous liquids comprising fatty acid glycol ester, alkyl
sulphate (or alkyl EO sulphate) and fatty acid dialkanolamide in specific ratios (triangular
figure) to obtain uniform products of low viscosity, beautiful appearance and temperature
stability. The level of the fatty acid dialkanolamide should be 3% or higher, in view
of satisfactory dispersing fatty acid glycol ester.
[0007] GB 1,230,413 teaches fatty acid glyol ester and fatty acid mono-alkylolamide as pearl
lustre formers in liquids and pastes. Page 2 lines 28-31 indicate that the level of
pearl lustre formers is increased with increasing surfactant levels.
[0008] Thus, there is a problem in providing a pearlescent effect using the organic pearlescers
in liquid compositions which contain reasonable quantities of PAS. Surprisingly, the
applicants have found that this problem can be overcome by using a small amount of
ABS or similar long-chain material or a nonionic surfactant in the formulation as
well. Since a primary reason for using PAS is to minimise the amount of ABS used,
clearly not too much of the latter should be used.
[0009] Thus the present invention provides a pearlescent liquid detergent composition comprising
an organic pearlescer, at least 5% weight of a primary alkyl sulphate anionic surfactant
characterised in that the composition further comprises less than 2.5% by weight of
a pearlescer crystallisation enhancer which is an acid, salt or alcohol having a hydrophobic
moiety with an average of at least 16 carbon atoms or alkylene oxide nonionic surfactant.
[0010] The hydrophobic moiety in the crystallisation enhancer may for example be an alkyl
group, an alkenyl group or an alkylbenzene group. In the latter case, the atoms of
the benzene ring are to be taken into account in the at least 16 carbon atoms. The
alkyl groups or alkenyl group may optionally be alkoxylated with one or more alkoxy
and/or propoxy groups. The acid group may be chosen from a wide class including the
sulphates, sulphonates and carboxylates, preferably sulphonates and carboxylates.
[0011] Another preferred class of pearlescer crystallisation enhancers comprises the soaps.
These are usually salts of alkali metals with fatty acids of appropriate chain length.
It is convenient to provide a soap by reaction
in situ, ie by incorporating both an appropriate alkali metal hydroxide and a fatty acid into
the composition. Suitable fatty acids include oleic acid, ricinoleic acid and fatty
acids derived from castor oil, rapeseed oil, groundnut oil, palmkernel oil or mixtures
thereof. The sodium or potassium soaps of these acids are preferred.
[0012] It is especially preferred to incorporate two or more pearlescer crystallisation
enhancers of different types, for example an alkylbenzene sulphonate and a soap.
[0013] The salts of the free acids are preferably the alkali metal, eg sodium or potassium,
or alkaline earth metal salts. Such salts may be added in the salt form
per se or formed
in situ in the composition, eg by reaction with the appropriate metal hydroxide. It will
be appreciated that many crystallisation enhancers are anionic or nonionic surfactants
(
vide infra).
[0014] In general, it is preferred that the hydrophobic moiety comprises on average at least
about 18 carbon atoms. Some preferred crystallisation enhancers are sodium C₁₁-C₁₅)
alkyl benzene sulphonates, stearic acid, sodium stearate, oleic acid and sodium oleate.
[0015] A further group of pearlescent enhancers according to the invention are the nonionic
surfactants.
[0016] Although the amount of crystallisation enhancer must be less than 2.5% by weight
of the total composition, preferably it is present at from 0.005% to 1.5% by weight,
especially from 0.01% to 1%.
[0017] Any organic pearlescer may be used in compositions according to the present invention.
Many examples will be known to persons skilled in the art but typical examples are
ethylene glycol monostearate and ethylene glycol distearate. Normally, only relatively
small amounts of pearlescer need to be incorporated to produce the desired pearlescent
appearance, for example from 0.1% to 5% by weight of the total composition, more especially
from 0.5% to 2.5%.
[0018] Preferably, the primary alkyl sulphate has an average at from 8 to 15 carbon atoms,
most preferably from 12 to 13. Although the amount of the primary alkyl sulphate constitutes
at least 5% by weight of the total composition, preferably it is present from 10%
to 20% by weight.
[0019] Compositions formulated according to the requirements defined in respect of the present
invention are generally suited as light duty liquids for washing delicate fabrics.
Therefore it is very much preferred to formulate them as aqueous compositions, especially
as isotropic aqueous compositions. To this end, a small amount of hydrotrope may be
incorporated, for example a low molecular weight alcohol.
[0020] The compositions of the present invention may also comprise a thickener, for example
a polymer such as a suitable acrylate, methacrylate (or co-polymer thereof) or a cellulose
such as hydroxymethyl cellulose. Typical inclusion levels of thickener are from 0.1%
to 10%, eg from 0.5% to 5% by weight of the total composition.
[0021] It is also preferred that for light duty compositions, the concentration of detergent
actives (soaps and non-soap surfactants) is not too high. For example, the amount
of actives may be from 10% to 30% by weight of the total composition, most preferably
from 15% to 25%.
[0022] Conversely, the amount of water will be relatively high, for example from 65% to
85%, most preferably from 70% to 80% by weight of the total compositions.
[0023] Many examples of such light duty compositions will be substantially free from inorganic
detergency builders. However, whether or not a soap is incorporated as a pearlescer
crystallisation enhancer, soaps may be included for other purposes. They may be regarded
as surfactants, fabric softeners or detergency builders since they demonstrate all
of these properties to a degree. In this capacity, soaps will usually be incorporated
in small amounts, for example from 0.5% to 2.5% by weight of the total composition.
Soaps included for these purposes may also be soaps of shorter chain-length fatty
acids such as that derived from coconut oil. They may be incorporated as soap
per se or formed
in situ.
[0024] As well as the crystallisation enhancer and the primary alkyl sulphate, it is also
possible to include other anionic non-soap surfactants in compositions according to
the present inventions. The non-soap anionic surfactants as a class (including any
chosen as crystallisation enhancers) are usually water-soluble alkali metal salts
of organic sulphates and sulphonates having alkyl radicals containing from about 8
to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of
higher acyl radicals. Examples of suitable synthetic anionic detergent compounds other
than those already mentioned are sodium alkyl glyceryl ether sulphates, especially
those ethers of the higher alcohols derived from tallow or coconut oil and synthetic
alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates
and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C₈-C₁₈)
fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the
reaction products of fatty acids such as coconut fatty acids esterified with isethionic
acid and neutralised with sodium hydroxide; sodium and potassium salts or fatty acid
amides of methyl taurine; alkane monosulphonates such as those derived by reacting
alphaolefin (C₈-C₂₀) with sodium bisulphite and those derived from reacting paraffins
with SO₂ and Cl₂ and then hydrolysing with a base to produce a random sulphonate;
and olefin sulphonates, which term is used to describe the material made by reacting
olefins, particularly C₁₀-C₂₀ alpha-olefins, with SO₃ and then neutralising and hydrolysing
the reaction product.
[0025] It is also preferred to include a nonionic surfactant in the composition. Where the
crystallisation enhancer is nonionic in character, it is still preferred to include
additional nonionic surfactant for its detergency properties. The amount of nonionic
surfactant included for detergency is preferably from 1% by weight to 15% by weight
of the total composition, most preferably from 2.5% to 10%.
[0026] Suitable nonionic surfactants which may be used include in particular the reaction
products of compounds having a hydrophobic group and a reactive hydrogen atom, for
example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially
ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds
are alkyl (C₆-C₂₂) phenols - ethylene oxide condensates, the condensation products
of aliphatic (C₈-C₁₈) primary or secondary, linear or branched alcohols with ethylene
oxide, and products made by condensation of ethylene oxide with the reaction products
of propylene oxide and ethylenediamine. Other so-called nonionic detergent compounds
include long-chain tertiary amine oxides, long-chain tertiary phosphine oxides and
dialkyl sulphoxides.
[0027] It is also possible to include organic detergency builders in the composition, for
example the alkali metal, ammonium and substituted ammonium polyacetates, carboxylates,
polycarboxylates, polyacetyl carboxylates and polyhydroxysulphonates. Specific examples
include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine-tetraacetic
acid, nitrilotriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic
acids and citric acid.
[0028] Apart from the ingredients already mentioned, a number of optional ingredients may
also be present, such as lather boosters, e.g. alkanolamides, particularly the monoethanolamides
derived from palmkernel fatty acids and coconut fatty acids, lather depressants, oxygen-releasing
bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach
precursors, chlorine-releasing bleaching agents such as trichloroisocyanuric acid.
However, for light duty applications, it is usually preferred to omit bleaches. Inorganic
salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent
agents, perfumes, enzymes such as proteases and amylases, germicides and colourants
may also be included.
[0029] A preferred process for preparing compositions according to the invention comprises
admixing at least some of the ingredients except the pearlescer and heating the resultant
composition, admixing the pearlescer in the molten state with the composition, followed
by cooling. Any other ingredients not included in the first admixing stage can be
incorporated at any convenient subsequent stage.
[0030] The present invention will now be illustrated by the following Examples.
EXAMPLE I
[0031]
EXAMPLES II-IV
[0032]
[0033] The above Examples clearly show that the compositions I-IV of the invention containing
a crystallisation enhancer were all pearlescent, whereas composition A despite the
pearlescer but without the invention was not pearlescent.
1. A pearlescent liquid detergent composition comprising an organic pearlescer, at least
5% by weight of a primary alkyl sulphate anionic surfactant characterised in that
the composition further comprises less than 2.5% by weight of a pearlescer crystallisation
enhancer selected from the group of acids, salts, alcohols and esters having a hydrophobic
moiety with an average of at least 16 carbon atoms or alkyene oxide nonionic surfactants.
2. A composition according to claim 1, wherein the hydrophobic moiety has at least 18
carbon atoms.
3. A composition according to claims 1 or claim 2, wherein the pearlescer crystallisation
enhancer is an alkylbenzene sulphonate.
4. A composition according to claim 1 or claim 2, wherein the pearlescer crystallisation
enhancer is a nonionic surfactant.
5. A composition according to claim 1 or claim 2, wherein the pearlescer crystallisation
enhancer is a soap.
6. A composition according to any of claims 1-5, comprising a mixture of ABS and soap
as pearlescer crystallisation enhancers.
7. A composition according to claims 1-6, wherein the amount of the pearlescer crystallisation
enhancer is from 0.005% to 1.5% by weight.
8. A composition according to claims 1-7, wherein the pearlescer is ethylene glycol monostearate
or ethylene glycol distearate.
9. A composition according to claims 1-8, wherein the amount of the pearlescer is from
0.1% to 5% by weight of the total composition.
10. A composition according to claim 1-9, wherein the amount of the primary alkyl sulphate
is from 10% to 20% by weight.
11. A composition according to claims 1-10, which composition is isotropic.
12. A composition according to claim 1-11, further comprising a thickener.
13. A composition according to claim 1-12, wherein the total amount of all detergent actives
is from 10% to 30% by weight of the total composition.
14. A composition according to claims 1-13, comprising from 65% to 85% by weight of water.
15. A composition according to claims 1-14, which composition is substantially free from
inorganic builder.
16. A composition according to claims 1-15, comprising from 1% to 15% by weight of nonionic
surfactant.
1. Eine perlende flüssige Detergenszusammensetzung, enthaltend ein organisches Perlmittel,
zumindest 5 Gewichtsprozent eines anionischen primären Alkylsulfat-Surfactants, dadurch gekennzeichnet, daß die Zusammensetzung ferner weniger als 2,5 Gewichtsprozent eines Perlmittelkristallisationserhöhers
enthält, ausgewählt aus der Gruppe von Säuren, Salzen, Alkoholen und Estern mit einem
hydrophoben Rest mit einem Durchschnitt von zumindest 16 Kohlenstoffatomen oder Alkylenoxidnichtionische
Surfactants.
2. Zusammensetzung nach Anspruch 1, worin der hydrophobe Rest zumindest 18 Kohlenstoffatome
aufweist.
3. Zusammensetzung nach einem der Ansprüche 1 oder 2, worin der Perlmittelkristallisationserhöher
ein Alkylbenzolsulfonat ist.
4. Zusammensetzung nach Anspruch 1 oder Anspruch 2, worin der Perlmittelkristallisationserhöher
ein nichtionisches Surfactant ist.
5. Zusammensetzung nach Anspruch 1 oder Anspruch 2, worin der Perlmittelkristallisationserhöher
eine Seife ist.
6. Zusammensetzung nach einem der Ansprüche 1 bis 5, enthaltend eine Mischung von ABS
und Seife als Perlmittelkristallisationserhöhern.
7. Zusammensetzung nach den Ansprüchen 1 bis 6, worin die Menge des Perlmittelkristallisationserhöhers
von 0,005 bis 1,5 Gewichtsprozent beträgt.
8. Zusammensetzung nach den Ansprüchen 1 bis 7, worin das Perlmittel Ethylenglykolmonostearat
oder Ethylenglykoldistearat ist.
9. Zusammensetzung nach den Ansprüchen 1 bis 8, worin die Menge des Perlmittels im Bereich
von 0,1 bis 5 Gewichtsprozent der Gesamtzusammensetzung liegt.
10. Zusammensetzung nach den Ansprüchen 1 bis 9, worin die Menge des primären Alkylsulfats
im Bereich von 10 bis 20 Gewichtsprozent liegt.
11. Zusammensetzung nach den Ansprüchen 1 bis 10, worin die Zusammensetzung isotrop ist.
12. Zusammensetzung nach den Ansprüchen 1 bis 11, die ferner ein Verdickungsmittel enthält.
13. Zusammensetzung nach den Ansprüchen 1 bis 12, worin die Gesamtmenge an allen detergentaktiven
Verbindungen im Bereich von 10 bis 30 Gewichtsprozent der Gesamtzusammensetzung liegt.
14. Zusammensetzung nach den Ansprüchen 1 bis 13, enthaltend von 65 bis 85 Gewichtsprozent
Wasser.
15. Zusammensetzung nach den Ansprüchen 1 bis 14, welche im wesentlichen frei von anorganischem
Builder ist.
16. Zusammensetzung nach den Ansprüchen 1 bis 15, enthaltend von 1 bis 15 Gewichtsprozent
nichtionisches Surfactant.
1. Composition détergente liquide opalescente comprenant un opalescent organique, au
moins 5% en poids d'un alkylsulfate primaire tensioactif anionique, caractérisée en
ce que la composition comprend en outre moins de 2,5% en poids d'un agent de renforcement
de la cristallisation opalescent choisi parmi les acides, les sels, les alcools, et
les esters ayant un fragment hydrophobe avec une moyenne d'au moins 16 atomes de carbone
ou des tensioactifs non ioniques oxyde d'alkylène.
2. Composition selon la revendication 1, dans laquelle le fragment hydrophobe a au moins
18 atomes de carbone.
3. Composition selon les revendications 1 ou 2, dans laquelle l'agent de renforcement
de la cristallisation opalescent est un alkylbenzènesulfonate.
4. Composition selon les revendications 1 ou 2, dans laquelle l'agent de renforcement
opalescent est un tensioactif non ionique.
5. Composition selon les revendications 1 ou 2, dans laquelle l'agent de renforcement
opalescent est un savon.
6. Composition selon l'une quelconque des revendications 1 à 5, comprenant un mélange
d'ABS et de savon comme agents de renforcement de la cristallisation opalescents.
7. Composition selon les revendications 1 à 6, dans laquelle la quantité d'agent de renforcement
de la cristallisation opalescent va de 0,005% à 1,5% en poids.
8. Composition selon les revendications 1 à 7, dans laquelle l'opalescent est le monostéarate
d'éthylène-glycol ou le distéarate d'éthylène-glycol.
9. Composition selon les revendications 1 à 8, dans laquelle la quantité d'opalescent
va de 0,1 à 5% en poids de la composition totale.
10. Composition selon les revendications 1 à 9, dans laquelle la quantité d'alkylsulfate
primaire va de 10 à 20% en poids.
11. Composition selon les revendications 1 à 10, cette composition étant isotrope.
12. Composition selon les revendications 1 à 11, comprenant en outre un épaississant.
13. Composition selon les revendications 1 à 12, dans laquelle la quantité totale de tous
les détergents actifs va de 10 à 30% en poids de la composition totale.
14. Composition selon les revendications 1 à 13, comprenant de 65 à 85% en poids d'eau.
15. Composition selon les revendications 1 à 14, cette composition étant sensiblement
exempte d'adjuvant minéral.
16. Composition selon les revendications 1 à 15, comprenant de 1 à 15% en poids de tensioactif
non ionique.